Certain polyepoxide treated amine modified thermoplastic phenol-aldehyde resins and method of making same



United States Patent Ofiiice 2,828,280 Patented Mar. 25, 1958 CERTAINPOLYEPOXIDE TREATED AMINE MODI- FIED THERMOPLASTIC PHENOL-ALDEHYDERESINS AND METHOD OF MAKING SAME Melvin De Groote, St. Louis, andKwan-Ting Shen, Brentwood, Mo., assignors to Petrolite Corporation,Wiimington, Del., a corporation of Delaware No Drawing.

Serial No. 338,574, now Patent No. 2,771,436, dated November 20, 1956.Divided and this application April 30, 1956, Serial No. 581,372

14 Claims. (Cl. 26053) The present invention is a continuation-in-partof our co-pending application. Serial No. 305,079, filed August 18,1952, now abandoned, and a division of our copending application SerialNo. 338,574, filed February 24,

in demulsification.

The products of our invention are obtained by the method of firstcondensing certain phenol-aldehyde resins, hereinafter described indetail, with a basic hydroxylated secondary monoamine, having not morethan 32 carbon atoms in any group attached to the amino nitrogen atom,35

and formaldehyde, which condensation is followed by reaction of theresin condensate with certain phenolic polyepoxides, also hereinafterdescribed in detail, and cogenerically associated compounds formed inthe preparation of the polyepoxides.

In preparing diepoxides or the low molal polymers one does usuallyobtain cogeneric materials which may include monoepoxides. However, thecogeneric mixture is invariably characterized by the fact that there ison the average, based on the molecular weight, of course, more than oneepoxide group per molecule.

A more limited aspect of the invention is represented by the reactionproduct of (A) an amine-modified phenolaldehyde resin condensate asdescribed, and (B) a member of the class of (1) compounds of thefollowing formula d and (2) cogenerically associated compounds formed inthe preparation of (l) preceding.

"or purpose of supplying information and also for purpose 7 if brevity.

Notwithstanding the fact that subsequent data will be Originalapplication February 24, 1953, lo

Our invention is also 25 presented in considerable detail, comessomewhat involved and certain facts should be kept in mind. Thecpoxides, and particularly the diepoxides may have no connecting bridgebetween the phenolic nuclei as in the case of a diphenyl derivative ormay have a variety of connecting bridges, i. e., divalent linkingradicals. Our preference is that either diphenyl compounds be employedor else compounds where the divalent link is obtained by the removal ofa carbonyl oxygen atom as derived from a ketone or aldehyde.

If it were not for the expense involved in preparing and purifying themonomer We would prefer it to any other form, i. e., in preference tothe polymer or mixture of polymer and monomer.

Stated another way, we would prefer to use materials of the kinddescribed, for example, in U. 5. Patent 2,530,353, dated November 14,1950. Said patent describes compounds having the general formula whereinR is an aliphatic hydrocarbon bridge, each 11 independently has one ofthe values 0 and l, and X is an alkyl radical containing from 1 to 4carbon atoms.

The list of patents hereinafter referred to in the text as far aspolyepoxide goes, is as follows:

yet the description be- U. S. Patent No. Dated Inventor 2,122,958 July5. 1938.. Schafer. 2,139,760...- December 13. 1938 Mlkeska et al.2,174,245 September 26. 1939 Do. 2.195.539 .c. April 2, i940 D0.2,207,719 July 16, 1940. Cohen et al. 2244021 w. une 3, 1941.. Rosen atal. 2.246.321 June 17. I941. Ro en. 2,285,5(13 June 9, i942 Britton eta1. 2,3313% October 12, 1943 Winning et a]. 2,430.00 \lo\ cm her 4,1947.. De Groom et a1. 2,457,329 Decemb r 28. 1948 Swern et a1.2,462,047 February 15, 1949- Wyler. 2362,0425 0 Do. 2,482,748 September27, 1949 Dletzler. 2,488,131 November 15. 1949..-- Mlkeska et al.2,503,190 Aprl] 4, 1950.. District at al. 2,504,031 April 11. 1950 Becket al. 2,506.486 May 2, 1950 Bender at al. 2,515,900 July 18, 1950..Stevens et; a]. 2,515,907. "do, Do. 2,515,908.. d() A D0. 2,526,545October 17, 1950. Dietzler.

530,353 November 14. 1950. Havens. 2,564,191 August l4. 195i Dc Grooteet a1. 2,575,553 Novem ber 20. 19510.. Newey et al. 2,58!,46 January 8,1952 Zech.

2,581,91 .d0 Albert. 2,582,985. January 22. 1952 Greenlee.

The compounds having two oxirane rings and employed for combination withthe reactive amine-modified phenolaldehyde resin condensates as hereindescribed are compounds of the following formula and cogenericallyassociated compounds formed in their preparation:

in which R represents a divalent radical selected from the class ofketone residues formed by the elimination of the ketonic oxygen atom andaldehyde residues obtained by the elimination of the aldehydic oxygenatom, the divalent radical in which R, R", and R'" represent a member ofthe class of hydrogen and hydrocarbon substituents of the aromaticnucleus, said substituent member having not over 18 carbon atoms; nrepresents an integer selected from the class of zero and l, and nrepresents a whole number not greater than 3. The above mentionedcompounds and those cogenerically associated compounds formed in theirpreparation are thermoplastic and organic solvent-soluble. Reference tobeing thermoplastic characterizes them as being liquids at ordinarytemperature or readily convertible to liquids by merely heating belowthe point of pyrolysis and thus differentiates them from infusibleresins. Reference to being soluble in an organic ill condensate) solventmeans any of the usual organic solvents, such as alcohols, ketones,esters, ethers, mixed solvents, etc. Reference to solubility is merelyto differentiate from a reactant which is not soluble and might be notonly insoluble but also infusible. Furthermore, solubility is a factorinsofar that it is sometimes desirable to dilute the compound containingthe epoxy rings before reacting with amine. In such instances, ofcourse, the solvent selected would have to be one which is notsusceptible to oxyalkylation, as for example, kerosene, benzene,toluene, dioxane, various ketones, chlorinated solvents, dibutyl ether,dihexyl ether, ethyleneglycol diethylether, diethyleneglycoldiethylether, and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The1,2-epoxy ring is sometimes referred to as the oxirane ring todistinguish it from other epoxy rings. Hereinafter the word "epoxyunless indicated otherwise, will be used to mean the oxirane ring, i.e., the 1,2-epoxy ring. Furthermore, where a compound has two or moreoxirane rings to as polyepoxides. They usually represent, of course,1,2-epoxide rings or oxirane rings in the alpha-omega position. This isa departure, of course, from the standpoint of strictly formalnomenclature as in the example of the simplest diepoxide which containsat least 4 carbon atoms and is formally described as1,2-epoxy-3,4-epoxybutane l,2-3,4-diepoxybutane) It well may be thateven though the previously suggested formula represents the principalcomponent, or components, of the resultant or reaction product describedin the previous text, it may somewhat similar compounds, generally ofmuch higher molecular weight, have been described as complex resinousepoxides which are polyether derivatives of polyhydric phenolscontaining an average of more than one epoxide group per molecule andfree from functional groups other than epoxide and hydroxyl groups. SeeU. S. Patent No. 2,494,295, dated January it), 1950, to Greenlee. Thecompounds here included are limited to the monomers or the low molalmembers of such series may be entirely free from a hydroxyl group. Thisis important because the instant invention is directed towards productswhich are not insoluble resins and have certain solubilitycharacteristics not inherent in the usual thermosetting resins. Note,for example, that said U. S. Patent No. 2,494,295 describes productswherein the epoxide derivative can combine with a sulfonamide resin. Theintention in said U. S. Patent 2,494,295, of course, is to obtainultimately a suitable resinous product having the characteristics of acomparatively insoluble resin.

Having obtained a reactant having generally 2 epoxy rings as depicted inthe last formula preceding, or low molal polymers thereof, it becomesobvious the reaction can take place with any amine-modifiedphenol-aldehyde resin by virtue of the fact that there is always presentreactive hydroxyl groups which are part of the phenolic nuclei and theremay be present reactive hydrogen atoms attached to a nitrogen atom, oran oxygen atom, depending on the presence of a hydroxylated group orsecondary amino group.

To illustrate the products which represent the subject matter of thepresent invention reference will be made to a reaction involving a moleof the oxyalkylating agent, i. e., the compound having two oxirane ringsand a condensate. Proceeding with the example previously described it isobvious the reaction ratio of two moles of the amine condensate to onemole of the oxyalkylating agent gives a product which may be indicatedas follows:

in which the various characters have their previous significance and thecharacterization condensate is simply an abbreviation for the condensatewhich is described in greater detail subsequently.

Such final product in turn also must be soluble but solubility is notlimited to an organic solvent but may include water, or for that matter,a solution of water containing an acid such as hydrochloric acid, aceticacid, hydroxyacetic acid, etc. In other words, the nitrogen groupspresent, whether two or more, may or may not they will be referred besignificantly basic and it is immaterial whether aqueous solubilityrepresents an anhydro base or the free base (combination with water) ora salt form such as the acetate, chloride, etc. The purpose in thisinstance is to differentiate from insoluble resinous materials,particularly those resulting from gelation or cross-linking. Not onlydoes this property serve to differentiate from instances where aninsoluble material is desired, but also serves to emphasize the factthat in many instances the preferred compounds have distinctwater-solubility or are distinctly dispersible in 5% gluconic acid. Forinstance, the products freed from any solvent can be shaken with 5 to 20times their weight of 5% distilled water at ordinary temperature andshow at least some tendency towards being self-dispersing. The solventwhich is generally tried is xylene. If xylene alone does not serve thena mixture of xylene and methanri, for instance, 80 parts of xylene and20 parts of methanol, or 70 parts of xylene and 30 parts of methanol canbe used. Some times it is desirable to add a small amount of acetone tothe be important to note that xylene-methanol mixture, for instance, 5%to 10% of acetone.

The polyepoxide treated condensates obtained in the manner describedare, in turn, oxyalkylatiOn-susceptible and valuable derivatives can beobtained by further reaction with ethylene oxide, propylene oxide,ethylene imine, etc.

Similarly, the polyepoxide-derived compounds can be reacted with aproduct having both a nitrogen group and generally contain two epoxiderings per molecule and and a 1,2-ep0xy group, such as3-dialkylaminoepoxypropane. See U. S. Patent No. 2,520,093, dated August22, 1950, to Gross.

Although the herein described products have a number of industrialapplications, they are of particular value for resolving petroleumemulsions of the water-in-oil type that are commonly referred to as cutoil," roily oil, emulsitied oil," etc., and which comprise fine dropietsof naturally-occurring waters or brines dispersed in a more or lesspermanent state throughout the oil which constituted the continuousphase of the emulsion.

The new products are useful as wetting, detergent and leveling agents inthe laundry, textile and dyeing industries; as wetting agents anddetergents in the acid washing of building stone and brick; as wettingagents and spreaders in the application of asphalt in road building andthe like; as a flotation reagent in the flotation separation of variousaqueous suspensions containing negatively charged particles, such assewage, coal washing waste water, and various trade wastes and the like;as germicides, insecticides, emulsifying agents, as, for example forcosmetics, spray oils, water-repellent textile finishes; as lubricants,etc.

As far as the use of the herein described products goes for purpose ofresolution of petroleum emulsions of the Water-in-oil type, weparticularly prefer to use those which as such or in the form of thefree base or hydrate, i. e., combination with water or particularly inthe form of a low molal organic acid salt such as the gluconates or theacetate or hydroxy acetate, have sufficiently hydrophile character to atleast meet the test set forth in U. S. Patent No. 2,499,368, dated March7, 1950, to De Groote et al. In said patent such test for emulsificationusing a water-insoluble solvent, generally xylene, is described as anindex of surface activity.

In the present instance the various condensation products as such or inthe form of the free base or in the form of the acetate, may notnecessarily be xylene-soluble although they are in many instances. Ifsuch compounds are not xylene-soluble the obvious chemical equivalent orequivalent chemical test can be made by simply using some suitablesolvent, preferably a water-soluble solvent such as ethylene glycoldiethylether, or a low molal alcohol, or a mixture to dissolve theappropriate product being examined and then mix with the equal weight ofxylene followed by addition of water. Such test is oh viously the samefor the reason that there will be two phases on vigorous shaking andsurface activity makes its presence manifest. It is understood thereference in the hereto appended claims as to the use of xylene in theemulsification test includes such obvious variant.

For purpose of convenience what is said hereinafter will be divided intonine parts with Part 3, in turn, being divided into three subdivisions:

Part 1 is concerned with our preference in regard to the polyepoxide andparticularly the diepoxide reactant;

Part 2 is concerned with certain theoretical aspects of diepoxidepreparation;

Part 3, Subdivision A, is concerned with the preparation of monomericdiepoxides, including Table I;

Part 3, Subdivision B, is concerned with the preparation of low molalpolymeric epoxides or mixtures containing low molal polymeric epoxidesas well as the monomer and includes Table II;

Part 3, Subdivision C, is concerned with miscellaneous phenolicreactants suitable for diepoxide preparation;

Part 4 is concerned with the phenolaldehyde resin which is subjected tomodification by condensation reaction to yield the amine-modified resin;

Part 5 is concerned with appropriate basic hydroxylated secondary amineswhich may be employed in the preparation of the herein-describedamine-modified resins;

Part 6 is concerned with reactions involving the resin,

. the amine, and formaldehyde to produce specific products .or compoundswhich are then subjected to reaction with polyepoxides;

Part 7 is concerned with the reactions involving the two preceding typesof materials and examples obtained by such reaction. Generally speaking,this involves nothing more than a reaction between 2 moles of apreviously prepared amine-modified phenol-aldehyde resin condensate asdescribed, and one mole of a polyepoxide so as to yield a new and largerresin molecule, or comparable product;

Part 8 is concerned with the resolution of petroleum emulsions of thewater-in-oil type by means of the previously described chemicalcompounds or reaction products; and

Part 9 is concerned with uses for the products herein described eitheras such or after modification, including any applications other thanthose involving resolution of petroleum emulsions of the water-in-oiltype.

PART 1 As will be pointed out subsequently, the preparation ofpolyepoxides may include the formation of a small amount of materialhaving more than two epoxide groups per molecule. if such compounds areformed they are perfectly suitable except to the extent they may tend toproduce ultimate reaction products which are not solventsoluble liquidsor low-melting solids. Indeed, they tend to form thermosetting resins orinsoluble materials. Thus, the specific objective by and large is toproduce diepoxides as free as possible from any monoepoxides and as freeas possible from polyepoxides in which there are more than two epoxidegroups per molecule. Thus, for practical purposes what is saidhereinafter is largely limited to polyepoxides in the form ofdiepoxides.

As has been pointed out previously one of the reactants employed is adiepoxide reactant. It is generally obtained from phenol(hydroxybenzene) or substituted phenol. The ordinary or conventionalmanufacture of the epoxides usually results in the formation of aco-generic mixture as explained subsequently. Preparation of the monomeror separation of the monomer from the remaining mass of the co-genericmixture is usually expensive. If mono mers were available commerciallyat a low cost, or if they could be prepared without added expense forseparation, our preference would be to use the monomer. Certain monomershave been prepared and described in the literature and will be referredto subsequently. However, from a practical standpoint one must weigh theadvantage, if any, that the monomer has over other low molal polymersfrom a cost standpoint; thus, we have found that one might as wellattempt to prepare a monomcr and fully recognize that there may bepresent, and probably invariably are present, other low molal polymersin comparatively small amounts. Thus, the materials Which are most aptto be used for practical reasons are either monomers with some smallamounts of polymers present or mixtures which have a substantial amountof polymers present. Indeed, the mixture can be prepared free frommonomers and still be satisfactory. Briefly, then, our preference is touse the monomer or the monomer with the minimum amount of higherpolymers.

It has been pointed out previously that the phenolic nuclei in theepoxide reactant may be directly united, or united through a variety ofdivalent radicals. Actually, it is our preference to use those which arecommercially available and for most practical purposes it meansinstances where the phenolic nuclei are either united directly withoutany intervening linking radical, or else united by a ketone residue orformaldehyde residue. The commercial bis-phenols available now in theopen market illustrate one class. The diphenyl derivatives illustrate asecond class, and the materials obtained by reacting substitutedmonofunctional phenols with an aldehyde illustrate the third class. Allthe various known classes may be used but our preference rests withthese classes due to their availability and ease of preparation, and

also due to the fact that the cost is lower than in other examples.

Although the diepoxide reactants can be produced in more than one way,as pointed out elsewhere, our preference is to produce them by means ofthe epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains onlya modest amount of polymers corresponds to the derivative of bis-phenolA. It can be used as such, or the monomer can be separated by an addedstep which involves additional expense. This pound of the followingstructure is preferred as the epoxide reactant and will be used forillustration repeatedly with the full understanding that any of theother epoxides described are equally satisfactory, or that the higherpolymers are satisfactory, or that mixtures of the monomer and higherpolymers are satisfactory. The formula for this compound is Referencehas iust been made to bis-phenol A and a suitable epoxide derivedtherefrom. Bis-phenol A is dihydroxy-diphenyl-dirnethyl methane, withthe 4,4 isomers predominating and with lesser quantities of the 2,2 and4,2 isomers being present. It is immaterial which one of these isomersis used and the commercially available mixture is entirely satisfactory.

Attention is again directed to the fact that in the instant part, towit, Part 1, and in succeeding parts, the text is concerned almostentirely with epoxides in which there is no bridging radical or thebridging radical is derived from an aldehyde or a ketone. It would beimmaterial if the divalent linking radical would be derived from theother groups illustrated for the reason that nothing more than meresubstitution of one compound for the other would be required. Thus, whatis said hereinafter, although directed to one class or a few classes,applies with equal force and effect to the other classes of epoxidereactants.

If sulfur-containing compounds are prepared they should be freed fromimpurities with considerable care for the reason that any time that alow-molal sulfurcontaining compound can react with epichlorohydrin therei may be formed a by-product in which the chlorine happened to beparticularly reactive and may represent a product, or a mixture ofproducts, which would be unusually toxic, even though in comparativelysmall concentration.

PART 2 The polyepoxides and particularly the diepoxides can be derivedby more than one method as, for example, the use of epichlorohydrin orglycerol dichlorohydrin. If a product such as bisphenol A is employedthe ultimate compound in monomeric form employed as a reactant in thepresent invention has the following structure:

Treatment with epichlorohydrin, for example, does not yield this productinitially but there is an intermediate produced which can be indicatedby the following structure:

,tated composition. The dim u y. stem om n mbe of sources and a few ofthe more important ones are as follows:

(1) The closing of the epoxy ring involves the use of caustic soda orthe like which, in turn, is an effective catalyst in causing the ring toopen in an oxyalkylation reaction.

Actually, what may happen for any one of a number of reasons is that oneobtains a product in which there is only one epoxide ring and there may,as a matter of fact,

be more than one hydroxyl radical as illustrated by the followingcompounds:

CHI H H H 1: H H H HC-O-C-O O--CC-CH H l H A A O OH: H l

HC-CCO O-C-CCH H E A (2) Even if one starts with the reactants in thepreferred ratio, to wit, two parts of epichlorohydrin to one part ofbis-phenol A, they do not necessarily so react and as a result one mayobtain products in which more than two epichlorohydrin residues becomeattached to a single bis-phenol A nucleus by virtue of the reactivehydroxyls present which enter into oxyalkylation reactions rather thanring closure reactions.

(3) As is well known, ethylene oxide in the presence of alkali, and forthat matter in the complete absence of water, forms cyclic polymers.Indeed, ethylene oxide can produce a solid polymer. This same reactioncan, and at times apparently does, take place in connection withcompounds having one, or in the present instance, two substitutedoxirane rings, i. e., substituted 1,2 epoxy rings. Thus, in many ways itis easier to produce a polymer, particularly a mixture of the monomer,dimer and trimer, than it is to produce the monomer alone.

(4) As has been pointed out previously, monoepoxides may be present and,indeed, are almost invariably and inevitably present when one attemptsto produce polycpoxides, and particularly diepoxides. The reason is theone which has been indicated previously, together with the fact that inthe ordinary course of reaction a diepoxide, such as H H H I H H H HC7OE[O C OIC: 1LC }CH 0 $113 0 may react with a mole of bis-phenol A togive a monoepoxy structure. Indeed, in the subsequent text immediatelyfollowing reference is made to the dimers, trimers and tetramers inwhich two epoxide groups are present. Needless to say, compounds can beformed which correspond in every respect except that one terminalepoxide group is absent and in its place is a group having one chlorineatom and one hydroxyl group, or else two hydroxyl groups, or anunreacted phenolic ring.

(5) Some reference has been made to the presence of a chlorine atom andalthough all effort is directed towards the elimination of anychlorine-containing molecule yet it is apparent that this is often anideal approach rather than a practical possibility. Indeed, the samesort of reactants are sometimes employed to obtain products in H whichintentionally there is both an epoxide group and a chlorine atompresent. See U. S. Patent No. 2,581,464, dated January 8, 1952, to Zech.

What has been said in regard to the theoretical aspect is, of course,closely related to the actual method of preparation which is discussedin greater detail in Part 3, particularly Subdivisicns A and B. Therecan be no clear line between the theoretical aspect and actualpreparative steps. However, in order to summarize or illustrate what hasbeensaid in Part 1, immediately preceding reference will be made to atypical example which already has been employed for purpose ofillustration. The particular exand also a hydroxyl group, one need go nofurther ample is to consider the reaction product of CH! OH: H H H (E HH H H H H A H H H W FF \"7 e /'ii Fit- O Ha O 0 33B; 0 It is obviousthat two moles of such material combine and bisphenol A in amole-for-mole ratio, since the inireadily with one mole of bisphenol A,tial reactant would yield a product having an unreacted epoxy ring andtwo reactive hydroxyl radicals. Referring g 19 again to a previousformula, consider an example where HO OH two moles of bisphenol A havebeen reacted with 3 moles (EH; of epichlorohydrin. The simplest compoundformed to produce the product which is one step further along, would bethus:

OH: 03 (3B1 O O w $5 H 41H; $11; H CH at least, towards polymerization.In other words, one Such a compound is comparable to othercompoundsprior example shows the reaction product obtained from havingboth the hydroxyl and epoxy ring such as 9,10-

one mole of the bisphenol A and two moles of epichloroepoxy octadecanol.The ease with which this type of hydrin. This product in turn wouldrepresent three moles compound polymerizes is pointed out by U. S.Patent o bisphenol A and four moles of epiqhlorohydrin- No. 2,457,329,dated December 28, 1948, to Swern et al.

For Purpose of brevity without gomg any further the The same difiicultywhich involves the tendency to next formula is in essence one which,perhaps in an ideale th art of com ounds havin a r activ ized way,establishes the composition of resinous products polymenz on e p p g e eavailable under the name of Epon Resins as now sold in ring and ahydrF'Xyl radical may illusirated by com; the open market. See, alsochemical pamphlet entitled pounds Where Instead of the oxmme rmg P YEpon Surface-Coating Resins, Shell Chemical Corporaring) there ispresent a l3'epoxy ring- Such compounds fi New York City The word is aregistered are derivatives of trimethylene oxide rather than ethylenetrademark of the Shell Chemical Corporation. oxide. See U. S. PatentsNos. 2,462,047 and 2,462,048

OH; OH CH: 5 e O O-GHr-GH-OH: O 01 H: JHI n' (311: is

For the purpose of the instant invention, n may repboth dated February15, 1949, to Wyler.

resent a number including zero, and at the most a low At the expense ofrepetition of what appeared prenumber such as 1, 2 0r 3- This ation doesi t viously, it may be well to recall that these materials may in actualefforts to obtain resins as difierentiated from val-y from i l solublgnonq'esinous to complex the herein describe? Soluble materials' It isJune Prob 5O soluble resinous epoxides which are polyether derivativesable that in the resinous products as marketed for coatof polyhydricphenols containing an average of more mg use h value of n, 13 wiuhstannany hlgher than one epoxide group per molecule and free fromfunc- Note again what has been said previously that any fortional groupsother thanj id d hydroxyl groups.

mula is, at best, an over-simplification, or at the most presentsperhaps only the more important or principal a, The former are hereincluded, but the latter, 1. e., highly resinous or insoluble types, arenot.

constituent or constituents. These materials may vary from simplenon-resinous to complex resinous epoxides In j 'y 111 8% Of W 8 fi n531d, comwhich are polyether derivatives of polyhydric phenols con-Pounds Sultabie for macho" with amlncs y b 8 mtaining an average of morethan one epoxide group per marized by the following formula:

molecule and free from functional groups other than or for greatersimplicity the formula could be restated epoxide and hydroxyl groups.thus:

H, H H: Hz 5H H: H:

Referring now to what has been said previously, to wit, in which thevarious characters have their prior significompounds having both anepoxy ring or the equivalent 7 cance and in which R 0 is the divalentradical obtained 11 by the elimination of a hydroxyl hydrogen atom and anuclear hydrogen atom from the phenol in which R, R", and R'" representa member of the TABLE I Ex- Patent ample Dlpheuol Diglycidyl etherrefernumber .ence

CHKOJLOH): D1(apexypropcxyphenyDmethane 2, 506,485 CH;CH((TeHt0 D t pypr p xyu r l t yl t an 506, 486 (CH3)7C(CQH40H)I. Di(epoxypropoxyphenyldimethylmethane. 2, 506, 486 CQH5C(CHAHC5H|ODi(epoxypropoxyphenyl)ethylmethylmethane 2, 506, 6 CQH5)1C(CUQOI1Di(epoxypropoxyphenybdiethylrnethane 2, 506, 456 H3C(C3H1)(CBII{OH)1Dl(epoxypronoxyphenyl)methylpropylmethane 2, 506, 486 CH3C(C H)(C@H4OHDl(epoxypropoxyphenyl)mcthylphenylmethane 2, 506, 486 cnncrcnm ctmomrDi(epoxypropoxyphenyl)ethylphenylmethane 2, 506, 486 CQHTOKIQHQ CeHlOHMDi(epoxypropoxyphenyl)propylphenylmethane. 2, 606, 486 C4lhC(CtIl )(CH40H)a Di(epoxypropoxyphenyl)butylphenylmethane. 2, 506,486 (CH CHQCHUHILOHM... Di(epoxypronnxyphenyl)tolylmethane 506,486(CIhC.H|)C(CHi)(CsHlOHh. Dl(epoxypropoxyphenyl)tolylmethylmethane. 2,506, 486 Dlhydrox dlphenyl 4,4'-bis(2,3-ep0xypr0p0xy)diphenyl 2, 530,353(CH;)C( H .C H|OH):2.2-1)is(4-(2,a-epoxypropoxyfltertiarybutylphenyl)propane- 2, 630,

class consisting of hydrogen and hydrocarbon substituents of thearomatic nucleus, said substituent member having not over 18 carbonatoms; n represents an integer selected from the class of zero and 1,and n' represents a whole number not greater than 3.

PART 3 Subdivision A The preparations of the diepoxy derivatives of thediphenols, which are sometimes referred to as diglycidyl Subdivision BTABLE II H C O-C -0Rr[R]..RiOCt J-C -0R -[Rln-RrOCC--O H: H H| Hi H: H:H H:

(in which the characters have their previous significance) Example RrO-from HR OH --R n 1:. Remarks number B1 Hydroxy benzene- CH: 1 0,1,2Phenol known as bis-phenol A. Low polymeric mixture about as or morewhere n'=0. remainder largely where (g =1, some where it'd.

B2 do CH; 1 0,1,2 Phenol known as bis-phenol B. See note regarding B1above. As,

B3 Orthobutylphenol CH: 1 0,1,2 Even though 1: is preferably 0, yet theusual reaction product might well 0011- tain materials where n is 1, orto a 8 lesser degree 2.

HA. Orthoamylphenol (Fin 1 0,1,2 Do.

B5 Orthooctylphenol (11H. 1 0,1,2 Do.

B6 Orthononylphenol CH| 1 0,1,2 Do.

I UH] B7 Orthododecylphenol CH; 1 0,1,2 Do.

Subdivision C TABLE Il-Contlnued Example -R O- from HmOH R- n 1: Remarksnumber 138 Metacresol CH: 1 0,1,2 See prlor note. This phenol used asinitial material is known as bis-phenol O. For other sultablebis-phenols see U. 8. Patent 2,564,191.

139 do 0H; 1 0,1,2 See prior note.

a CHI 1310...--. Dlbntyl (orthopara) phenol- 1g 1 0,1,2 Do.

1311.....- Dlamyl (ortho-pera) phenol. 1g 1 0,1, 2 Do.

1512....-- Dloctyl (ortho-pam) phenol- 15 l 0,1,2 Do

1313--.--- DlnonyHortho-pera) phenol. I6 1 0,1,2 Do.

2814.-.-.. Dlamyl (ortho-para) phenolg l 0. 1,2 Do.

315...... .---do I5 1 0,1,2 Do.

1316 Hydroxy benzene.--...-.--- Z 1 0,1,2 Do.

2817....-. Dlemyl phenol (ortho-pnra). B-8 1 0,1,2 Do.

1318 on S-- 1 0,1,2 Do.

B19.-... Dibuty phenoltortho-pera)- g 13 1 0,1,2 Do.

B20 do I! H 1 0 1.2 Do.

H H v 821...... DlnonylphonoHortho-para)- 1 g 1 0,1,2 Do.

1322...--. Hydroxy benzene (i? 1 0,1,2 Do.

32L do Noun 0 0, 1, 2 D0.

1 h 1-.-..- CH 1 1 2 Bee prior note. (Astopreparatlon ohm- Buonhopisopmpy p we lsupropylldene bls-(Zisopropylphenol) see U. 8. PatentNo. 2,482,748, dated & Sept. 27, 1949, to Dletzler.)

h l -CH B-GH 1 1 2 See prior note. (As to re oration of the 325rm-octylp mo i phenol sulfide see Patent No. 2,488,!34. dated NOV. 15,1949, $0 Mlkeeke at at.) V H CH 1 2 Seeprlor note. (Asto re ratlonof theB26 benzene phenol sulfide see Patent No.

phenolic nuclei. For purpose of illustration attention is directed tonumerous other diphenols which can be readily convened to a suitablepolyepoxide, and particularly diepoxide, reactant.

As previously pointed out the initial phenol may be substituted, and thesubstltuem group in turn may be a cyclic up c s the abou o pe le t x m"?as in the instance;of' cyclohexylphenql or phenylphenol.

gardless of the nature of the bond between the two 7 Such substituentsare usually in the ortho position and may be illustrated by a phenol ofthe following composition:

no on Similar phenols which are monofunctional, for instance, paraphenylphenol or paracyclohexyl phenol with an additional substituent in theortho position, may be employed in reactions previously referred to, forinstance, with formaldehyde or sulfur chlorides to give comparablephenolic compounds having 2 hydroxyls and suitable for subsequentreaction with epichlorohydrin, etc.

Other examples include:

wherein R is a substituent selected from the classconsisting ofsecondary butyl and tertiary butyl groups and R, is a substituentselected from the class consisting of alkyl, cycloalkyl, aryl, aralkyland alkaryl groups, and wherein said alkyl group contains at least 3carbon atoms. See U. S. Patent No. 2,515,907.

CI Il OCHIOCI u ClHu 'sHn in which the -C H groups are secondary amylgroups. See U. 8. Patent No. 2,504,064.

See U. S. Patent No. 2,503,196.

whereink is a-member of the group eonsisting-of-alkyl,

and' kw y fllkyl-contining from l'to 5 carbon atoms, inclusive, and aryland chloraryl radicals of the benzene series. See U. S. Patent No.2,526,545.

OH OH R: R1 31 B1 A.

wherein R, is a substituent selected from the class consisting ofsecondary butyl and tertiary butyl groups and R, is a. substituentselected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl,and alkaryl groups. See U. S. Patent No. 2,515,906.

CH=CH OH C H OK See U. S. Patent No. 2,515,908.

As to sulfides, the following compound is of interest:

ed t: 05 1:

See U. S. Patent No. 2,331,448.

As to descriptions of various suitable phenol sulfides, reference ismade to the following patents: U. S. Patents Nos. 2,246,321, 2,207,719,2,174,248, 2,139,766, 2,244,- 021, and 2,195,539.

As to sulfones, see U. 8. Patent No. 2,122,958.

As to suitable compounds obtained by the use of formaldehyde or someother aldehyde, particularly compounds such as Alkyl Alkyl Alkyl A inwhich R is a methylene radical, or a substituted methylene radical whichrepresents the residue of an aldehyde and is preferably theunsubstituted methylene radical derived from formaldehyde. See U. S.Patent N0. 2,430,002.

See also U. 8. Patent No. 2,581,919 which describes di(dialkyl cresol)sulfides which include the monosulfides, the disulfides, and thepolysulfides. The following formula represents the various dicresolsulfides of this invention:

OH OH CHI CHI in which R, and R are alkyl groups, the sum of whosecarbon atoms equals 6 to about 20, and R and R, each preferably contain3 to about 10 carbon atoms, and x is l to 4. The term sulfides" as usedinthis text, therefore, includes monosulfide, disulfide, andpolysulfidcs.

PART 4 It is well knownthat one can readily purchase on the open market,or prepare, fusible, organic solventsoluble, water-insoluble resinpolymers of a composition approximated in an idealized form by theformula on on on n 11 -K Io O a n n R n n In the above formula nrepresents a small whole number varying from 1 to 6, 7 or 8, or more, upto probably it] or 12 units, particularly when the resin is subjected toheating under a vacuum as described in the literature. A limitedsub-genus is in the instance of low molecular weight polymers where thetotal number of phenol nuclei varies from 3 to 6, i. e., It varies from1 to 4; R represents an aliphatic hydrocarbon substituent, generally analkyl radical having from 4 to carbon atoms, such as a butyl, amyl,hexyl, decyl or dodecyl radical. Where the divalent bridge radical isshown as being derived from formaldehyde it may, of course, be derivedfrom any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it isnecessarily soluble in any organic solvent.

This is particularly true where the resins are derived fromtrifunctional phenols as previously noted. However, even when obtainedfrom a difunctional phenol, for instance paraphenylphenol, one mayobtain a resin which is not soluble in a nonoxygenated solvent, such asbenzene, or xylene, but requires an oxygenated solvent such as a lowmolal alcohol, dioxane, or diethyleneglycol dicthylether. Sometimes amixture of the two solvents (oxygenated and nonoxygenated) will serve.See Example 9a of U. 5. Patent No. 2,499,365, dated March 7. 1950, to DeGroote and Keiser.

The resins herein employed as raw materials must be soluble in anonoxygenated solvent, such as benzene or xylene. This presents noproblem insofar that all that is required is to make a solubility teston commercially available resins, or else prepare resins which arexylene or benzene-soluble as described in aforementioned U. S. PatentNo. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, toDe Groote and Keiser. In said patent there are describedoxyalkylation-susceptible, fusible, non-oxygenated-organicsolvent-soluble, water-insoluble, low-stage phenolaldehyde resins havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule. These resins are difunctional onlyin regard to methylol-forming reactivity, are derived by reactionbetween a difunctional monohydric phenol and an aldehyde havin not over8 carbon atoms and reactive toward said phenol and are formed in thesubstantial absence of trifunctional phenols. The phenol is of theformula in which R is an aliphatic hydrocarbon radical having at least 4carbon atoms and not more than 24 carbon atoms, and substituted in the2,4,6 position.

If one selected a resin of the kind just described previously andreacted approximately one mole of the resin with two moles offormaldehyde and two moles of a basic nonhydroxylated secondary amine asspecified, following the same idealized over-simplification previouslyreferred to, the resultant product might be illustrated thus:

18 The basic nonhydroxylated amine may be designed thus:

RI HN In conducting reactions of this kind one does not necessarilyobtain a hundred percent yield for obvious reasons. Certain sidereactions may take place. For instance, 2 moles of amine may combinewith one mole of the aldehyde or only one mole of the amine may combinewith the resin molecule, or even to a very slight extent, if at all, 2resin units may combine without any amine in the reaction product, asindicated in the following formulas:

OH OH OH 0H OH H H H H H C- C- C C C H H H H H R n R R R n As has beenpointed out previously, as far as the resin unit goes one can use a moleof aldehyde other than formaldehyde, such as acetaldehyde,propionaldehyde or butyraldehyde. The resin unit may be exemplifiedthus:

R R R in which R' is the divalent radical obtained from the particularaldehyde employed to form the resin. For reasons which are obvious thecondensation product obtained appears to be described best in terms ofthe method of manufacture.

As previously stated the preparation of resins, the kind herein employedas reactants, is well known. See previously mentioned U. S. Patent2,499,368. Resins can be made using an acid catalyst or basic catalystor a catalyst having neither acid nor basic properties in the ordinarysense or without any catalyst at all. It is preferable that the resinsemployed be substantially neutral. In other words, if prepared by usinga strong acid as a catalyst, such strong acid should be neutralized.Similarly, if a strong base is used as a catalyst it is preferable thatthe base be neutralized although we have found that sometimes thereaction described proceeded more rapidly in the presence of a smallamount of a free base. The amount may be as small as at 200th of apercent and as much as a few lOths of a percent. Sometimes moderateincrease in caustic soda and caustic potash may be used. However, themost desirable procedure in practically every case is to have the resinneutral.

in preparing resins one does not get a single polymer, i. e., one havingjust 3 units, or just 4 units, or just 5 units, or just 6 units, etc. Itis usually a mixture; for instance, one approximating 4 phenolic nucleiwill have some trimer and pentarner present. Thus, the molecular weightmay be such that it corresponds to a fractional value for n as, forexample, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for usingother than those which are lowest in price and most readily availablecommercially. For pur poses of convenience suitable resins arecharacterized in the following table:

TABLE III Position of R Phenyl Tertiary butyl Secondary butyl.Gyelohexyl. P Tertiary amyl Mixed secondary and tertiary amyl.

Doriecyl Tertiary butyl d Tertiary amyl Non Tertiary butyl Tertiary amylNnnyl Tertiary butyl.

Tertiary amyl. Nonyl Tertiary butyl Tertiaram i Propionalgehyde.

PART As has been pointed out previously the amine herein employed as areactant is a basic hydroxyiated secondary monoamine whose compositionis indicated thus:

R! in which R represents a monovalent alkyl, alicyclic, andalkyl radicalwhich may be hetcrocyclic in a few instances as in a secondary aminederived from furfurylamine by reaction of ethylene oxide or propyleneoxide. Furthermore, at least one of the radicals designated by R musthave at least one hydroxyl radical. A large number of secondary aminesare available and may be suitably employed as reactants for the presentpurpose. Among others, one may employ dicthanolamine, methylethanolamine, dipropanolamine and ethylpropanolamine. Other suitablesecondary amines are obtained, of course, by taking any suitable primaryamine, such as an alkylamine, an arylaikylamine, or an alicyclic amine,and treating the amine with one mole of an oxyalkylating agent, such asethylene oxide, propylene oxide, butylcne oxide, glycide, ormethylglycide. Suitable primary amines which can be so converted intosecondary amines, include butylamine, amylamine, hexylamine, highermolecular weight amines derived from fatty acids, cyclohexylamine,benzylamine, furfuryiamine, etc. In other instances secondary amineswhich have at least one hydroxyl radical can be treated similarly withan oxyalkylating agent, or, for that matter, with an alkylating agentsuch as benzylchloride, esters of chloracetic acid, alkyl bromides,dimethyisulfate, esters of sulfonic acid, etc., so as to convert theprimary amine into a secondary amine. Among others, such amines includeZ-amino-l-butanol, Z-amino- 2-methyl-1-propanol,Z-amino-Z-methyl-1,3-propanediol, Z-amino-Z-ethyl-1,3-propanediol, andtris-(hydroxymethyl)-aminomethane. Another example of such amines isillustrated by 4-amino-4-methyl-2-pentanol.

Similarly, one can prepare suitable secondary amines which have not onlya hydroxyl group but also one or more divalent oxygen linkages as partof an ether radical. The preparation of such amines or suitablereactants for preparing them has been described in the literature andparticularly in two United States patents, to wit, U. S. Patents Nos.2,325,514, dated July 27, 1943, to Hester, and 2,355,337, dated August8, 1944, to Spence. The latter patent describes typical haloalkyl ethcrssuch as CHaOCzHiCl CHr--CH= CiH O CJHLO CQHAO (151140 Carlee] Suchhaloalkyl ethers can be reacted with ammonia or with a primary aminesuch as ethanolamine, propanolamine, monoglycerylarnine, etc., toproduce a secondary amine in which there is not only present a hydroxylradical but a repetitious ether linkage. Compounds can be readilyobtained which are exemplified by the following formulas:

(CaHsO CzHiO C2114) HO CIHI (Calif/ C 1 4 2 0 GIHI) HOCaHa (OHIO CHaOHnOCHiCHaOCHsCH!) HO CIHI (CHsO C HICH'OHICHCHICH) a NH HO.CH:.C .CH:OHl

CHz.C.OHiOH in; CHn-CH OH emma 21 See, also, corresponding"hydroxylatdamines which'can "be' obtained from rosin or similar raw materials anddescribed in U.'Sl Patent No. 2;S10,063, dated June 6,1950, to Bried.Still other examples are illustrated by treatment 'of certain secondaryamines, such .as the following, with 'a'mole of an oxyalkylating agentas described; phenoxy- "ethylamine, phenoxypropylamine,phcnoxyalphamethylethylarnine, and phenoxypropylamine.

Other procedures for production of suitable compounds having a hydroxylgroup and asingle basic amino nitrogen atom can be obtained from anysuitable alcohol or the like by reaction with a reagent which containsan epoxide group and asecondary amine group."',Such reactantsarejdescribedjfor example, in U. S. PatentsNos.

1,977,251 and 1,977,253, both dated October 16, 1934, to Stallmann.Among the reactants described insaid latter jpatent arethe'following:

y, r PARTG The 'p oducts obtained by the herein described processes"representcogeneric mixtures which are the'resulrof a condensationreaction or reactions. Since the resin molecule cannot-be definedsatisfactorily by formula, although it may be so illustrated in anidealized simplification, it is diflicult to actually depict the finalproduct-bf the co'genericrnixture except in" termsofftheiproces'sjitself.

'PreViO u S: reference has *been' made to thefac'tftlia t the "procedureherein employed is coin'parablefiu a; way, to that vvhich borrespondstosomewhat similai aie rivatives' nia'de either from phenbls asdifierentiatedfrom a resin, '6r ln themanufactureof 'aphenol-aminefalde- "hyde rsinfor else from a particularly selected resinand "'an amine and formaldehyde in the manner 'descfibd-in"Bruson*Patent No.2,031,557 inorder to obtainwheatreactive resin. -Sincethe condensation productsobtained are not' heat-convertible and since**manufactu'reis' not restricted to a single phase system, and'sincetemperatures up to 150 C. orthereabouts may be employed, it is obvious I'that "the? procedure becomesf comparativlyfisimple. Indeed, perhaps no*description is -*necessary over and 'above what has been saidpreviously, in light of subsequent examples. However, for purposeof"clarity the following detailsare included.

A convenient-piece of'equipment for preparation of these cogenericmixtures is a resin pot of"the'-'kind de scribed in aforementioned U.S.Patent"No.2,'499,368. In most instances the resin selected is notapttobe a fusible liquid at theearly=-or low temperature stage ofreaction if employed as subsequently described; in fact, usually itisf'apt'vto be azsolid at idistinctly higheitemperatures, for instance,-ordinary room temperature. Thus, We have found it convenient to-use asolvent andqpar- -'ticularly one which can be: removed readily at a oom-I paratively moderate temperature, for instance, at 150 .13. Asuitablesolvent is usually benzene, xylenepor a cotnparable petroleumhydrocarbon or a mixture of isuch or similar solvents. 'Indeedpresinswhich are not soluble ';exceptin oxygenated solvents or mixturescontaining such 'solvents jarenot 'here 'included asiravvjmaterials.""'I :he reaction can be"co'nducted' issues a way-that th -gains!reaction, and perhaps the .bulk of the reactionjfititkes Place in apolyph'ase'system. "However,iftie si'rable, one

22 canuse"anoxygenated solvent such as a low-boiling"alcohol, including-ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or onecan use a comparatively non-volatile solvent such as dioxane or thediethyl- 5 ether of ethyleneglycol. One can also use a mixture ofbenzene 'or xylene and such oxygenated solvents. Note that the use ofsuch oxygenated solvent is not required in the sense that it is notnecessary to use an initial resin which is soluble only insin-oxygenated solvent as just noted, and it is not necessary to have asingle phase sys tem for reaction.

Actuallyfwater -is'apt to-be present as a solvent for the reason that'in rnost cases aqueous formaldehyde is lerriployed, vvhiclimaybe thecommercial product which is approximately"37%,- or it may be diluteddown to about formaldehyde. "However, paraformaldehyde can be usedbnt'it isrnoredifiicult perhaps to add asolid material instead-oflhe liquidsolution and,-everything-else "being equal, the latter is apt to be moreeconomical. 1 In 20 anyeventfwater is present as water'of reaction. Ifthe 1 solvent'is completely removed at the end of the process,"noproblem is involved if the material is used for any "subsequentreaction. "However, if the reaction mass is going to'be subjected tosome furtherreaction wherethe 2'5 solventfmay be objectionable as in'thecase of ethylor -hexyl alcohoh'and if there is to be subsequentoxyalkylat.ion,'"then, bhviously,-the alcohols should not be used *or*else itshoilldbe removed. The'fact that an oxygenated "solvent need-notbe employed, of course, is an advantage :0" for reasons stated.

Another'factonasfar as the selection of solvent goes, "is'whether ornotthecogeneric mixture obtained atthe "end ofthe reaction is to be used assuch or in the salt form. Thecoeneric mixtures obtained are-apt to besolids-or' 'thick viscous liquids'in which there is some change fromthe'initial--resin itself, particularly if some iof thednitialsblvent"is aptjtoremain Without complete removal. Even ifone starts witha resinwhich is almost water-til hite' infcolor, the products 'obtained arealmost lo invariably ada'rk red in color 02f at least a red amber," or

' "sticky-"and more tacky than' th'e" original'r'esiriitselffDe- .15pendingon the resin selected and on the amineselected 'the condensationproduct or 'reac'tionunass on asolvent- "ffreebasis may be hard,resinous and 'comparable to" the resin itself. l f f1 jTheproductsobtained, depending on-the reactants selected, may be water-insoluble,or water dispersible, or water-soluble, or close to being water-soluble.Water solubility'is' enhanced, of course,-by making a solution 'inthe-acidified vehicle such as a dilute solution, for instance, 'a'5%solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc. Onealso may convert the finished product into salts by simply adding astoichiometric amount ofany selected acid and removing any water presentby refluxing with benzene or the like. In 'fact the selection of thesolvent employed may depend in part Whether or not the product at thecompletion of the "reaction is to be converted into a salt form.

' m the'next succeeding paragraph it is pointed out that frequently itis convenient to eliminate all solvent, using "tifltemperature 6f 1 notover 1 150 C. and employing vactilitnflif required. Thisapplies, ofcourse, only to those circumstances where it is desirable or necessaryto *remove the solvent. 'Petroleum solvents, aromatic solvents, etc. canbe used.- "The 'selection'of'solvent, such aslbenzene, xylene, or thelike, depends primarily 'fon"cost,"i.-e.," the use" at 'the mosteconomical solvent and also on' three other factors,=gtwo ofwhichihaveween haehtibndiffb) is fthe solvent to remain in'fithe"i'eactiori mass withdut'frempval zirbr is the metronome e tbis ted weewmavhiasea 75"tdtidiincefan"alcoholfeither'low essay or l'righ boih ing,might interfere as in the case of oxyalky1atiQn?;and

the third factor is this, a is orti :to be made. to

, purify the reactionmass by the usual procedure as; for example, awater-wash to remove any unreacted, low I molal soluble amine, ifemployed and present after reerally speaking, such fa: procedure ismuch, lesssa'tisfa'caction? Such procedures are well known and, needlessto say, certain solvents are more suitable than others. Everything elsebeing equal, we have found xylene the most satisfactory solvent. A ig...

We have found no ,particularadvantage in using a to because even herewater of reaction is formed.

low temperature in the early stage of the reaction because, and forreasons explained, this. is not necessary although it does apply in someother procedures that, in a general way, bear some similarity to thepresent procedure. the reaction an opportunity to proceed as far as itwill at some low temperatuIe for instance, to but ultimately one mustemploythe higher temperature in :order to obtain products; of the kindhereindescribed. If a lower temperature reactionjs usegl initiallythepegu .J q is fie ii l f s i m l clannh nsr m.

few hours up to 24 hours. Wehavenotfound any case "where it wasnecessarypr even desirable ;t o ho1d;,the

low temperature stage for more than 2411011158. In. fact, we are notconvinced therejsany advantage in holding it at this stage for more than3 or 4' hoursat the most.

This, again, is a matter of convenience largely for one reason, Inheating and.;stirr ing thereactionmass there isat'endency forformaldehyde to be 1QSL ,-,ThllS,-lf the reaction can be conductedat alowertemperature, -then;.0 the amqunt of n e ets kfynnalns rd ia.d sreeedi v h nt ra c! m s ed; easmgn rsvqntl ny lessmi ler again. h s wer.mssra uren n eascsss m uuru out but may be convenient under certaincircumstances. 4

,On the other hand, if the, products are not mutually soluef u o v rt ilne arsstie slnreis r dlt .m' -ii If v ms a d. mstantaeress rts sa. heaan I n P od ct o r a ti m t all so b e ac tation isrequired, onlyto,the. extent that it helps cooling on helps distribution of theincoming formaldehyde... This -mutual {solubility is apt necessary aspreviously pointed ble then agitation should be more vigorous for thereason that reaction probably takes place principally at the interfacesand the more vigorous the agitation the more interfacial area. Thegeneraltprocedure employed is invariably the same when adding the resinand the se- ,lected solvent, such as benzene or-xylene.

R n n should be long enough to insure that the resin added, preferablyin a powdered form, is completely soluble.

However, if the resin is prepared as such it may be added 5 in solutionform, just as preparation is described in afore- -mentioned U. S. Patent2,499,368. After the resin is in complete solution the amine is addedand stirred. De-

pending ontheamine selected, it may or may not be soluble in,theresimsolution. if it is not soluble inthe resin solution it may bevsoluble in the aqueous formaldehyde solution. If so,.the'res in thenwill dissolve, in the formaldehyde solution as added, and if not, it iseven possible that the initial reaction mass could be athree- 1 phasesystem instead ofa two-phase system although this would be extremielyunusual This solution,,-or mechanical mixture, if notcompletely, solubleis cooled j to at least the reactiontemperature or somewhat below,

for example 35' C. or slightly lower, provided this. initial lowtemperature stage is employed. The formaldehyde 6 is then added in asuitable form. For reasons pointed out we prefer to use a solution andwhether to use a commercial 37% concentration is simply a matter of welargefscale choice. In large scale manufacturing there may be some ispresent, is another index.

6i) illustration.

There is no objection, of course, to giving ls tur'e, for instance,after holding the reaction mass with 25 the water of reaction and thewater of solution of the formaldehyde is eliminated. We then permit thetemperature to rise to somewhere about C., and generally slightly above100 C, and below C., by eliminating the solvent or part of the solventso the reaction mass stays within this predetermined range. This periodof heating and refluxing, after the water is eliminated, is continueduntil the reaction mass is homogeneous and en-.19 ne to reehourslensmfie emandf solvents is conducted in a conyentional manner-sin thesamqway as the'remoyal oli solve ts in resinmanufactureasdescribed inaforementioned U. S. Patent No.

Needless to say, as as the ratio of reactants goes we have invariablyemployed approximately one mpleof 0 the resin based on the molecularweight of the resin molecule, 2 moles of the seconda ry amine and 2moles of formaldehyde. In some-,instanfces we havefi dcd a trace ofcaustic as an added eatalyst; but have found no particular advantage inthis. ,In other cases wehave used a 45' slight excess offormaldehydeand, again, have not found any particular advantage in thisIn other cases we have a d a slight excess o m n a a nrhav t qun anyparticular advantage in so doing. Whenever feasible we have checked thecompleteness of reaction in the usual 0 ,ways, including the amount ofwater of reaction, molecuis: weight, and particularly in some, instanceshave checked whether or not the end-product. showed surface activity,particularly in a dilute acetic acid solution. The nitrogen contentafter removal of unreacted amine, if any In light of what has beenis aidprevio usly, littlenitire need be said as to the actual procedureemployed for the preparation of the herein described. condensationproducts. The following example will serve by way of E xample 1b 1 Thephenol-aldehyde resin is the one that has been identifiedpreviouslyasExample 2a. It was obtained from 5 a para-tertiary butylphenol andformaldehyde. The resin was prepared using an acid catalyst which wascompletely neutralized at the end of the reaction. The molecular weightof the resin was 882.5, This correspondedto an average of-about 3%phenolic nuclei, as the value for n advantage in using a 30% solution offormaldehyde but 70 which excludes the 2 external nuclei, i. e., theresin was apparently this is not true on a small laboratory scale orpilot plant scale. 30% formaldehyde may tend to decrease anyformaldehyde loss or make it easier to con- Q "1 a]! l in H, A if thereisforl n- 882 grams-of the resin identified as 2a preceding were f resinso obtained in a neutral state had a lightamber color.

powdered and mixed with 700 grams of xylene. The mixture was refluxeduntil solution was complete. It was then adjusted to approximately to C.and 210 grams of diethanolamine added. The mixture was stirredvigorously and formaldehyde added slowly. The formaldehyde used was a37% solution and 160 grams were employed which were added in about 3hours. The mixture was stirred vigorously and kept within a temperaturerange of 30 to C. for about 21 hours. At the end of this period of timeit was refluxed, using a phaseseparating trap and a small amount ofaqueous distillate withdrawn from time to time and the presence ofunreacted formaldehyde noted. Any unreacted formaldehyde seemed todisappear within approximately 3 hours after the refluxing was started.As soon as the odor of form- 15 aldehyde was no longer detectible thephase-separating trap was set so as to eliminate all water of solutionand reaction. After the water was eliminated part of the xylene wasremoved until the temperature reached about 150 C. The mass was kept atthis higher temperature for about 3% hours and reaction stopped. Duringthis time any additional water, which was probably water of reactionwhich had formed, was eliminated by means of the trap. The residualxylene was permitted to stay in the cogeneric mixture. A small amount ofthe sample was heated on a water bath to remove the excess xylene andthe residual material was dark red in color and had the consistency of asticky fluid or a tacky resin. The overall reaction time was a littleover 30 hours. In other instances it has varied from approximately 24 to36 hours. The time can be reduced by cutting the low temperature periodto about 3 to 6 hours.

Note that in Table IV following there are a large number of addedexamples illustrating the same procedure.

TABLE IV Strength of Reac- Reac- Mex Ex. Resin Amt, iormal- Solvent usedtlon tlon dis- No. used grs. Amine used and amount dehyde and amt.terxn, time till.

soln. and (hrs) tern amt. 882 Diethauolamlne, 210 g 37%, 162 g...Xylene, 700 5.-.. 22-26 32 137 480 Diethanolamiue, 105 g 37%, 81 gXylene, 450 g.- 21-23 28 150 633 ..dn Xylene, 600 g.-.. 20-22 36 145 441Dlpropan 30%, g... Xylene, 400 g.-.. 20-23 34 146 480 do Xy]eue,45(l g-2l-23 24 141 6b--." 633 .do Xylene, 600 g- 21-28 24 7b 2a 882Ethylethanolamlne,178 Xylene, 700 g 20-26 24 152 80"... Ba... 480Ethylethanolamlne, 89 g. Xylene, 450 gm- 24-30 28 151 9b 1Dn: 633 .doXylene, 600g 22-25 27 147 10b... 13a 473 Cyelohexylethanolamlne, 143 gyne, 450 21-31 31 146 11b. 14a 511 .(10 dO 22-23 36 148 126... 1541-. 665do Xylene, 550 g 20-24 27 152 CEHLOCBHAOCiHI 1317... 2a 441 NH, 176 g.do Xylene, 400 g..-. 21-25 24 HOCzI-l] CaHsOCzH OC2H4 146--.- Ga... 480NH, 176 g (1O Xylene, 450 g.... 20-26 26 146 HGCsHl C2 aOC2Ht0Cz t 9a..595 NH, 176 g do...- Xylene, 550 gm. 21-27 30 147 HOCzHtOCzHqOCzH;

-- 2a---" 441 NH, 192 g ..do Xylene, 400 g.... 20-22 30 148 HOCaHHOCIHIOCaHtOCaHt 5a... 480 NH, 192g "do c.d0 20-25 28 150 HOCQHIHOCBHLOC2H40C2H4 186---- 140-... 511 NH, 192 g "do Xylene, 500 g 21-2432 149 HOCzHi HOCzHrOCzHHOCzI-It 19b 2211-.-. 498 NH, 192 g do Xylene,450 2.--. 22-25 32 153 HOCzHi CHI 0C2H03 200---. 230-.-. 542 NH, 206 g30%, 100 g... Xylene, 500 g 21-23 36 151 HOO2H4 l( lHl)! 2115....250.... 647 NH, 206 g d0 ..do 25-30 34 148 HOCZHA CHI 0CBHI I 22L-..2a"... 441 NH, 206 g -110 Xylene, 400 g 22-23 31 146 HOCaHt 230--.-2611.-.- 595 Decylethanolamlne, 201 g 37%, 81 g Xylene, 500 g-..- 22-2724 145 246--.. 270..-- 391 Decy1ethanolam1ne,100g 30%,50 gm. Xylene, 300g 21-25 26 147 27 In each case the initial mixture was stirred and heldat a fairly low temperature (30 to 40 C.) for a period of several hours.Then refluxing was employed until the odor of formaldehyde disappeared.After the odor of formaldehyde disappeared the phase-separating trap wasemployed to separate out all the water, both the solution andcondensation. After all the water had been separated enough xylene wastaken out to have the final product reflux for several hours somewherein the range of 145 to 150 C., or thereabouts. Usually the mixtureyielded a clear solution by the time the bulk of the water, or all ofthe water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24examples in Table IV.

PART 7 The products obtained as herein described by reactions involvingamine condenstates and diglycidyl ethers or the equivalent are valuablefor use as such. This is pointed out in detail elsewhere. However, inmany instances the derivatives obtained by oxyalkylation are even morevaluable and from such standpoint the herein described products may beconsidered as valuable intermediates. Subsequent oxyalkylation involvesthe use of ethylene oxide, propylene oxide, butylene oxide, glycide,etc. Such oxyalkylating agents are monoepoxides as differentiated frompolyepoxides.

It becomes apparent that if the product obtained is to be treatedsubsequently with a monoepoxide which may require a pressure vessel asin the case of ethylene oxide, it is convenient to use the same reactionvessel in both instances. In other words, the 2 moles of theamine-modified phenol-aldehyde resin condensate would be reacted with apolyepoxide and then subsequently with a monoepoxide. In any event, ifdesired the polyepoxide reaction can be conducted in an ordinaryreaction vessel, such as the usual glass laboratory equipment. This isparticularly true of the kind used for resin manufacture as described ina number of patents, as for example, U. S. Patent No. 2,499,365.

Cognizance should be taken of one particular feature in connection withthe reaction involving the polyepoxide and that is this; theamine-modified phenol-aldehyde resin condensate is invariably basic andthus one need not add the usual catalysts which are used to promote suchreactions. Generally speaking, the reaction will proceed at asatisfactory rate under suitable conditions without any catalyst at all.

Employing polyepoxides in combination with a nonbasic reactant the usualcatalysts include alkaline materials such as caustic soda, causticpotash, sodium methylate, etc. Other catalysts may be acidic in natureand are of the kind characterized by iron and tin chloride. Furthermore,insoluble catalysts such as clays or specially prepared mineralcatalysts have been used. If for any reason the reaction does notproceed rapidly enough with the diglycidyl ether or other analogousreactant, then a small amount of finely divided caustic soda or sodiummethylate could be employed as a catalyst. The amount generally employedwould be 1% or 2%.

It goes without saying that the reaction can take place in an enertsolvent, i. e., one that is not oxyalkylation-susceptible. Generallyspeaking, this is most conveniently an aromatic solvent such as xyleneor a higher boiling coal tar solvent, or else a similar high boilingaromatic solvent obtained from petroleum. One can employ an oxygenatedsolvent such as the diethylether of ethylene glycol, or the diethyletherof propylene glycol, or similar ethers, either alone or in combinationwith a hydrocarbon solvent. The selection of the solvent depends in parton the subsequent use of the derivatives or reaction prodmts. If thereaction products are to be rendered solvent-free and it is necessarythat the solvent be readily removed as, for example, by the use ofvacuum distillation, thus xylene or an aromatic petroleum will serve. Ifthe product is going to be subjected to oxyalkylation subsequently, thenthe solvent should be one which is not oxyalkyladon-susceptible. It iseasy enough to select a suitable solvent if required in any instancebut, everything else being equal, the solvent chosen should be the mosteconomical one.

Example Ir:

The product was obtained by reaction between the diepoxide previouslydesignated as diepoxide 3A, and condensate 2b. Condensate 2b wasobtained from resin 51:. Resin 5a in turn was obtained from tertiaryamylphenol and formaldehyde. Condensate 2b employed as reactants resin5a and diethanolamine. The amount of resin employed was 480 grams; theamount of diethanolamine employed was grams, and the amount of 37%formaldehyde employed was 81 grams, and the amount of solvent (xylene)employed was 450 grams. All this has been described previously.

The solution of the condensate in xylene was adjusted to a 50% solution.In this particular instance, and in practically all the others whichappear in the subsequent table, the examples are characterized by thefact that no alkaline catalyst was added. The reason is, of course, thatthe condensate as such is strongly basic. If desired, a small amount ofan alkaline catalyst could be added, such as finely powdered causticsoda, sodium methylate, etc. If such alkaline catalyst is added it mayspeed up the reaction but it also may cause an undesirable reaction,such as the polymerization of a diepoxide.

In any event, 119 grams of the condensate dissolved in approximately anequal amount of xylene were stirred and heated to 100 C., and 17 gramsof diepoxide previously identified as 3A and dissolved in an equalweight of xylene were added dropwise. An initial addition of the xylenesolution carried the temperature to about 108 C. The remainder of thediepoxide was added in approximately an hours time. During this periodof time the reaction rose to about 126 C. The product was allowed toreflux at approximately C. to 130 C. using a phase-separating trap. Asmall amount of xylene was removed by means of this phase-separatingtrap so the reflux temperature rose gradually to about C. The mixturewas then refluxed at 180 C. for approximately 5 hours until the reactionstopped and the xylene which had been removed during the reflux periodwas returned to the mixture. A small amount of material was withdrawnand the xylene evaporated on a hot plate in order to examine thephysical properties. The material was a dark red viscous semi-solid. Itwas insoluble in water, it was in soluble in a 5% gluconic acid solutionbut was soluble in xylene and particularly in a mixture of 80% xyleneand 20% methanol.

However, if the material was dissolved in an oxygenated solvent and thenshaken with 5% gluconic acid it showed a definite tendency to disperse,suspend, or form a sol, and particularly in a xylene-methanol mixedsolvent as previously described, with or without the further addition ofa little acetone.

The procedure employed of course is simple in light of what has beensaid previously and in effect is a procedure similar to that employed inthe use of glycide or methylglycide as oxyalkylating agents. See, forexample, Part 1 of U. S. Patent No. 2,602,062, dated July 1, 1952, to DeGroote.

29 Various examples obtained in substantially the same manner areenumerated in the following tables:

may be employed to replace the diepoxides hereindescribed. However, suchderivatives are not included as TABLE V Cou- Die Time Max. Ex. den-Amt., or! e Amt, Xylene, Molar of reac- Dem Color and physical state No.sate grs. used grs. grs. ratio tlon, used hrs.

10-.-. 119 3A 17 135 2:1 180 Dark viscous semi-solid. 20.. 125 3A 17 1422:1 5 180 Do. -30.... 108 3A 17 125 2:1 5 185 Do. 116 3A 17 133 2:1 5180 Do. 50.... 126 3A 17 143 2:1 5 190 Do. 5D., 164 3A 17 181 2:1 6 180Dark solid mass. 7 126 3A 17 143 2:1 0 190 Do. .SC.... 143 3A 17 160 2:16 190 Do. 90. 140 3A 17 157 2:1 0 195 Do. 10 152 3A 17 169 2: 1 6 190Do.

TABLE VI Con- Die Time Max. nEx. den- Amt., 011 e Amt Xylene, Molar oireacternm, Color and physical state No. sate grs. used grs. g'rs. ratiotion,

used hrs.

l D' V 119 B1 27. 5 146. 5 2: 1 5 185 Dark viscous semi-solid. 2D 125 B127. 5 152. 5 2:1 7 188 D0. BD 108 B1 27. 5 135. 5 2:1 6 180 Do. 4D 116B1 27. 5' 143. 5 2:1 6 182 Do. n, D 126 B1 27. 5 153. 5 2:1 8 185 Do.

, D 164 B1 27. 5 191. 5 2:1 8 190 Dark solid mass. 713.... 13b 125 B127.5 153.5 221 7 180 Do. 18D.-. 48b 143 B1 27. 5 170. 5 2:1 8 184 D0.QB"; 19!) 140 B1 27.5 167. 5 2:1 8 185 Do. 0 L200 152 B1 27.5 179.5 2:18 190 Do.

"Sblubility in regard to all these compounds was sub- "slaniially'similar to that which was described in Example -'iC.

TABLE VII Probable Probable Resin conmol. wt of Amt. of Amt. of numberof Ex. No. densate reaction product, solvent, hydroxyls used productgrs. grs. per molecule TABLE VIII 5o Probable I Probable r Resin conmol.wt. of Amt. oi Amt. 01 number of Ex. I20. densnte reaction product,solvent, hydroxyls used product g'rs. grs. per molecule At this point itmay be desirable to direct attention .to two facts, the first being thatwe are aware that other diepoxide's free from an aromatic radical as,for example, L'epoxides derived from ethylene glycol, glycerine, or thepart of the instant invention.

At times we have found a tendency for an insoluble mass to form or atleast to obtain incipient cross-linking or gelling even when the molalratio is in order of 2 moles of resin to one of diepoxide. We have foundthis can be avoided by any one of the following procedures or theirequivalent. Dilute the resin or the diepoxide, or both, with an inertsolvent, such as xylene or the like. In some instances an oxygenatedsolvent, such as the diethyl ether of ethyleneglycol may be employed.Another procedure which is helpful is to reduce the amount of catalystused, or reduce the temperature of reaction by adding a small amount ofinitially lower boiling solvent such as benzene, or use benzeneentirely. Also, we have found it desirable at times to use slightly lessthan apparently the theoretical amount of diepoxide, for instance toinstead of PART 8 Conventional demulsifying agents employed in thetreatment of oil field emulsions are used as such, or after dilutionwith any suitable solvent, such as water, petroleum hydrocarbons, suchas benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc.Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethylalcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexylalcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneoussolvents such as pine oil, carbon tetrachloride, sulfur dioxide extractobtained in the refining of petroleum, etc., may be employed asdiluents. Similarly, the material or materials employed as thedemulsifying agent of our process may be admixed with one or more of thesolvents customarily used in connection with conventional demulsifyingagents. Moreover, said material or materials may be used alone or inadmixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in awater-soluble form, or in an oil-soluble form, or in a form exhibitingboth oiland water-solubility. Sometimes they may be used in a form whichexhibits relatively limited oil-solubility. However, since such reagentsare frequently used in a ratio of 1 to 10,000

or 1 to 20,000, or 1 to 30,000, or even lto 40,000, or

l to 50,000 as in desalting practice, such an apparent insolubility inoil and water is not significant because said reagents undoubtedly havesolubility within such concentrations. This same fact is true in regardto the material or materials of our invention when employed asdemulsifying agents.

The materials of our invention, when employed as treating ordemulsifying agents, are used in the conventional way, well known to theart, described, for example, in Patent 2,626,929, dated January 27,1953, Part 3, and reference is made thereto for a description ofconventional procedures of demulsifying, including batch, continuous,and down-the-hole demulsification, the process essentially involvingintroducing a small amount of demulsifier into a large amount ofemulsion with adequate admixture with or without the application ofheat, and allowing the mixture to stratify.

As noted above, the products herein described may be used not only indiluted form, but also may be used admixed with some other chemicaldemulsifier. A mixture which illustrates such combination is thefollowing:

The product of the present invention, for example, the product ofExample 2C, 20%.

A cyclohexylamine salt of a polypropylated naphthalene monosulfonicacid, 24%;

An ammonium salt of a polypropylated naphthalene monosulfonic acid, 24%

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol, 5%.

The above proportions are all weight percents.

PART 9 The products herein described as such and prepared in accordancewith this invention can be used as emulsifying agents for oils, fats andwaxes, as ingredients in insecticide compositions, or as detergents andwetting agents in the laundering, scouring, dyeing, tanning andmordanting industries. They may also be used for preparing boring ormetal-cutting oils and cattle dips, as metal pickling inhibitors, andfor pharmaceutical purposes.

Other uses include the preparation or resolution of petroleum emulsions,whether of the water-in-oil type or oil-in-water type. They may be usedas additives in connection with other emulsifying agents; they may beemployed to contribute hydrotropic effects; .they may be used asanti-strippers in connection with asphalts; they may be used to preventcorrosion, particularly the corrosion of ferrous metals for variouspurposes and a particularly in connection with the production of oil andgas, and also in refineries where crude oil is converted into. variouscommercial products. The products may be used industrially to inhibit orstop micro-organic growth or other objectionable lower forms of life,such as the growth of algae or the like; they may be used to inhibit thegrowth of bacteria, molds, etc.; they are valuable additives tolubricating oils, both those derived from petroleum and syntheticlubricating oils, and also to hydraulic brake fluids of the aqueous ornon-aqueous type, some have definite anti-corrosive action. They may beused also in connection with other processes where they are injectedinto an oil or gas well for purpose of removing a mud sheath, increasingthe ultimate flow of fluid from the surrounding strata, and particularlyin secondary recovery operations using aqueous flood waters. They canalso be used in dry cleaners soaps.

With regard to the above statements, reference is made -,drophilecharacter can be either increased or decreased and, inversely, thehydrophobe character can be decreased or increased. For example,neutralizing the product with practically any low molal acid, such asacetic acid, hydroxy-acetic acid, lactic acid, or nitric acid, is apt tomarkedly increase the hydrophile efiect. One may also use acids of thetype RO-CH,-CH,-0CH,CH;OCH,COOH in which R is a comparatively smallalkyl radical, such as methyl, ethyl or propyl. The hydrophile efiectmay be decreased and the hydrophobe eflect increased by neutralizationwith a monocarboxy detergent-forming acid. These are acids which have atleast 8 and not more than 32 carbon atoms. They are obtained from higherfatty acids and include also resin acids such as abietic acid, aridpetroleum acids such as naphthenic acids and acids obtained by theoxidation of wax. One can also obtain new products having uniqueproperties by combination with polybasic acids, such as diglycolic acid,oxalic acid, dimerized acids from linseed oil, etc. The most commonexamples, of course, are the higher fatty acids having generally 10 to18 carbon atoms. We have found that a particularly valuableanti-corrosive agent can be obtained from any suitable resin andformaldehyde provided the secondary amine is dicyclohexylamine. Thecorrosion-inhibiting properties of this compound can be increased byneutralization with either one or two moles of an oil-soluble sulfonicacid, particularly a sulfonic acid of the type known as mahoganysulfonic acid.

The oil-soluble sulfonic acids previously referred to may besynthetically derived by sulfonating olefins, aliphatic fatty acids, ortheir esters, alkylated aromatics or their hydroxyl derivatives,partially hydrogenated; aromatics, etc., with sulfuric acid or othersulfonating agents. However, the soaps of so-called mahogany acids whichare usually produced during treatment of lubricating oil distillateswith concentrated sulfuric acid or higher concentration) remain in theoil after settling out sludge. These sulfonic acids may be representedas umOs om where (R),, is one or more alkyl, alkaryl or aralkyl groupsand the aromatic nucleus may be a single or condensed ring or apartially hydrogenated ring. The lower molecular weight acids can beextracted from the acid treated oil by adding a small amount of water,preferably after dilution of the oil with kerosene. HOWEVBI'yflIO moredesirable high molecular weight (350-500) acids, particularly thoseproduced when treating petroleum distillates with fuming acid to producewhole oil, are normally recovered as sodium soaps by neutralim'ng theacid oil with sodium hydroxide or carbonate and extracting with aqueousalcohol. The crude soap extract is first recovered as a water curd afterremoval of alcohol by distillation and a gravity separation of some ofthe contaminating salts (sodium carbonate, sulfates and sulfites). Thesematerials still contain considerable quantities of salts andconsequentlyare normally purified by addition of a more concentrated alcoholfollowed by storage to permit settling of salt brine. The alcohol andWater are then stripped out and the sodium salts so obtained convertedinto free acids.

Not only can one obtain by-product sulfonic acids of the mahogany typewhich are perfectly satisfactory and within the molecular range of 300to 600 but also one can obtain somewhat similar materials which areobtained as the principal product of reaction and have all the usualcharacteristics of normal by-product sulfonic acids but in someinstances contain two sulfonic groups, i. e., are disulfonic acids. Thistype of mahogany acid, or better still, oil-soluble sulfonic acid, isperfectly satisfactory for the above described purpose.

Much of what has been said previously is concerned with derivatives inwhich the hydrophile properties are 33 enhanced in comparison with theresin as such, A procedure designed primarily to enhance the hydrophobeproperties of the resin involves derivatives obtained by a phenyl orsubstituted phenyl glycidyl ether of the strucin which R represents ahydrocarbon substituent such as an alkyl radical having 1 to 24 carbonatoms, or a cyclic group, such as a cyclohexyl group, a phenyl group, ora benzyl group, and n represents 0, 1, 2 or 3. n is zero in the instanceof the unsubstituted phenyl radical. Such compounds are in essenceoxyalkylating agents and reaction involves the introduction of ahydrophobe group and the formation of an alkanol hydroxyl radical.

As far as the use of the herein described products goes for purpose ofresolution of petroleum emulsions of the water-in-oil type, weparticularly prefer to use those which as such or in the form of thefree base or hydrate, i. e., combination of water or particularly in theform of a low molal organic acid such as the acetate or hydroxyacetate,havesufliciently hydrophile character to at least meet the test setforth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Grooteet a]; In said patent such test for emulsification using awater-insoluble solvent, generally xylene, is described as an index ofsurface activity.

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent is: g 1. The method of (A) condensing (a) anoxyalkylalion-susceptible, fusible, non-oxygenated organicsolventsoluble, water-insoluble, low-stage phenol-aldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being difunctional onlyin regard to methylolforming reactivity; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and reactive toward absence of trifunctionalphenols; said phenol being of the formula in which R is an aliphatichydrocarbon radical having at least 4 and not more than 24 carbon atomsand substituted in the 2,4,6 position; (b) a basic hydroxylatedsecondary monoamine having not more than 32 carbon atoms in any groupattached to the amino nitrogen atom, and (c) formaldehyde; saidcondensation reaction being conducted at a temperature sutfictently highto eliminate water and below the pyrolytic point of the reactants andresultants of reaction; and with the proviso that the resinouscondensation product resulting from the process be heat-stable andoxyalkylation-susceptible; followed by (B) reacting said resincondensate with a phenolic polyepoxide containing at least two 1,2-epoxyrings and being free from reactive functional groups other than 1,2-epxyand hydroxyl groups and cogenerically associated compounds selected fromthe class consisting of ketone. residues formed by the elimination ofthe ketonie oxygen atom,

,said phenol; said resin being formed in the substantial and thedivalent disulfide radical SS; said phenolic portion of the diepoxidebeing obtained from a phenol of the structure in which R, R", and 12'"represent a member of the class consisting of hydrogen and hydrocarbonsubstituents ofthe"aroriiatic nucleus, said substituent member havingnot" over"18 carbon atoms; with the .further proviso that said reactivecompounds (A) and (B) be members of the class consisting ofnon-thermosetting organic solvent-soluble liquids' and low-meltingsolids; with the added proviso that the reaction product be a member ofthe class o f solvent-soluble liquids and low-melting solids; saidreaction between (Aland (B) being conducted below the pyrolytidpoint ofthe reactants and the resultants of reaction; and with thefin'al'proviso that the ratio'of reactants be approximately 2 moles'ofthe resin condensate per mole of the phenolic polyepoxide.

2. The method of (A) condensing (a) an oxyalkylatitan-susceptible,fusible, non-oxygenated organic solvent- "soluble water-insoluble,low-stage phenol-aldehyde resin having an average molecular weightcorresponding to at least} and not over 6 phenolic nuclei per resinmolecule; said resin being difunctional only in regard to methy'lolformng reactivity; said resin being derived by reaction between adifunctional monohydric phenol and an' alde hyde having not over 8carbon atoms and reactive toward said phenol; said resin being formed inthe'substantial absence of trifunctional phenols; said phenol being ofthe "formula L ,in which R is an aliphatic hydrocarbon radical having atleast 4 and not more than 24 carbon atoms and substitutcd in the 2,4,6position; (b) a basic hydroxylated secondary monoamine having not morethan 32 carbon atoms in any group attached to the amino nitrogen atom,and (c) formaldehyde; said condensation reaction being conducted at atemperature sufi'iciently high to eliminate 'water and below thepyrolytic point of the rea'ctants and resultants of reaction; and withthe proviso that the resinous condensationproduct resulting from theprocess be heat-stable and oxyalkylation-susceptible; followed by (B)reacting a phenolic diepoxide containing two 1,2-epoxy rings and beingfree from reactive functional groups other than 1,2-epoxy and hydroxylgroups, and cogenerically associated compounds formed in the preparationof said diepoxides; said epoxides being selected from the classconsisting of (aa) compounds where the phenolic nuclei are directlyoined without an intervening bridge radical, and (bb) compoundscontaining a radical in which 2 phenolic nuclei are joined by a divalentradical selected from the class consisting of ltetone residues formed bythe elimination of the ketonic oxygen atom, and aldehyde residuesobtained by the elimination of the aldehydic oxygen atom, the divalentradical the divalent III t uinni.i r..iarr. ii d. Rf" re se a l therclass consistingof hydrogen and hydrocarbon substituents saitharsteafisn dsu ,said,s b s mh th v notgirerAS, canon atoms; the molarratio of reactant le s-$9 rs ta uBt ein approximately. ,2 tel sspectiyely; with the further proviso that saidreactive gorrtpoundst ljind(B) be members of the class consisttn of pon thermosetting organicsolvent-soluble 30 liquil sf arid flow-melting solids; with the finalproviso reaction product be a member of the class so vent-solubleliquids and low-melting solids; and said l rga c on between (A) and B)being conducted below the pyro ytic point of the reactants and the'resultants of re- -q, in on w a if steal h se s s (a) an k atttet aasmila slfi t s av e sdr Organic sch msqluhlg, yvgt eiginsgluble,low-stage phenol-aldehyde resin avir ig an-a verage molecular weightcorresponding to at jlea'stj and notover 6 phenolic n'uclei per resinmolecule; 'sa itj tjesm being difunctional only in regard to methylol-,form ng reaqtivityg said resin being derived by reaction ,between adifnnctibnal rironohydric phenol and an aldezltl dsi a t a' qt xsru c rbatoms n ti ikar said p enol said resin being formed in the substantialabsence of trit'unational'phenols; said phenol being of the formula i inlw hi ch' ik is janf all haticliyiirobarbbn' radical having at'least 4and not li'it'uri:than '24 cai'bon atoms and subtionof the'kefonic'o'itygen win an aldehyde "retinitis r5 m 6 0 obtained by theelimination of the aldchydic oxygen atom, the divalent radical *H H thedivalent i 10 radical, the divalent snlfone radical, and the divalentmonosulfidc radical -S the divalent radical -=-cH,scH,-=- and thedivalent disultide radical -*SS; and R Oi's 5 the divalent radicalobtained by the elimination of a hydro'xyl hydrogen atom and a nuclearhydrogen atom from the phenol i I, III

invvhich R, R", and R'" represent a 'member of the-classconsistihg"of"liydrogen' and hydrocarbon substituet'its of the aromaticiiucle'us, said substitue'iit member having not fover l8 'caibbnti'tomsfn 'represehts an integer selected from theclass-bf iero and l,aiid it represents a whole number not heater than 3i-ai1d (bb)cogenerically associated compounds formed in the preparation of (an)preceding, including monoepoxidcs; the molar ratio ofreactant-(A) toreactant "(13) being-approximately 2 to 1 respectively; with the furtherproviso that said reactive compoundsKAj and (B) be members of theclass-consistihg or nbaanermusemn organic solvent-soluble {liquids and'lbw fiielting' solids, with the finalproviso that the reactioit'pi'orlti'ci be s mmer-sf the class of solvent- 5 sollibledifiihtisflfiddow n'ieltih'gfidlidsf ana'said reaction *between fth) (B) being*ii'ondubted below "the p6iiifi6f the teac'ttirits h'nd reshl'tants *ofheat:-

l' 'l lrein'eiliod'of (A) condensing (a) an o'xyalkyla- Ltioii-siTsc'epiiUleTfusibk, "non-oxygenated organic solventsolilbl'e,wzi'tei -insohibleg tow-stage phenol-aldehyde resin having an averagemolecular weight corresponding toat least 3 and not over 6 phenolicnuclei per resin molecule;

said resin being' difunctional only in regard to methylolformingreactivity; said resin being derived by reaction between a difunctionalinonohydric phenol and an alde- 5 hyde having not over 8 carbon atomsand reactive toward said phenol; said resin being formed in thesubstantial U bsence of trifunctionalphenols; said phenol being of theormhla in which R is an' alit'ihatic hydrocarbon radical having at least4"andno't more than 24 carbon atoms and substituted'in the 2316position; (b) a basic hydroxylated sec ondary monoarnlne having not morethan 32 carbon atoms in any group attached to the amino nitrogen atom,

and (0) formaldehyde; said condensation reaction being conductedtemperaturefsufficiently high toeliminate and below "the pyrolytic pointof the reactants and baiittgpjsstig firodt icfresulting from theprocessbe lfiaflsialile and oxyalkylation-suseptible; renewed by RIIwherein R is an aliphatic hydrocarbon bridge, each n independently hasone of the values to 1, and R is an alkyl radical containing from 1 to12 carbon atoms, and (bb) cogenerically associated compounds formed inthe preparation of (aa) preceding, including monoepoxides; with theproviso that (B) consist principally of the monomer as distinguishedfrom other cogeners; the molar ratio of reactant (A) to reactant (B)being approximately 2 to 1 respectively; with the further proviso thatsaid reactive compounds (A) and (B) be members of the class consistingof non-thermosetting organic solvent-soluble liquids and low-meltingsolids; with the final proviso that the reaction product be a member ofthe class of solvent soluble liquids and low-melting solids; and saidreaction between (A) and (B) being conducted below the pyrolytic pointof the reactants and the resultants of the reaction.

5. The method of (A) condensing (a) an oxyalkylation-susceptible,fusible, non-oxygenated organic solventsoluble, water-insoluble,low-stage phenol-aldehyde resin having an average molecular Weightcorresponding to at least 3 and not over 6 phenolic nuclei per resinmolecule; said resin being difunctional only in regard tomethylolforming reactivity; said resin being derived by reaction betweena difunctional monohydric phenol and an aldehyde having not over 8carbon atoms and reactive toward said phenol; said resin being formed inthe substantial absence of trifunctional phenols; said phenol being ofthe formula in which R is an aliphatic hydrocarbon radical having atleast 4 and not more than 24 carbon atoms and substituted in the 2,4,6position; (b) a basic hydroxylated secondary monoamine having not morethan 32 carbon atoms in any group attached to the amino nitrogen atom,and (c) formaldehyde; said condensation reaction being conducted at atemperature sufficiently high to eliminate water and below the pyrolyticpoint of the reactants and resultants of reaction; and with the provisothat the resinous condensation product resulting from the process beheat-stable and oxyalkylation-susceptible; followed by (B) reacting amember of the class consisting of (aa) compounds of the followingformula and (bb) cogenerically associated compounds formed in thepreparation of (aa) preceding, including monoepoxides; with the provisothat (B) consist principally of the monomer as distinguished from othercogeners; the molar ratio of reactant (A) to reactant (B) beingapproximately 2 to 1 respectively; with the further proviso that saidreactive compounds (A) and (B) be members of the class consisting ofnon-thermosetting organic solvent-soluble liquids and low-meltingsolids; with the final proviso that the reaction product be a member ofthe class of solvent-soluble liquids and low-melting solids; and saidreaction between (A) and (B) being conducted below the pyrolytic pointof the reactants and the resultants of reaction.

6. The method of claim 1 wherein the precursory phenol contains at least4 and not over 14 carbon atoms in the substituent radical.

7. The method of claim 1 wherein the precursory resin contains at least4 and not over 14 carbon atoms in the substituent radical and theprecursory aldehyde is formaldehyde.

8. The product obtained by the method described in claim 1.

9. The product obtained by the method described in claim 2.

10. The product claim 3.

11. The product obtained by the method described in claim 4.

12. The product claim 5.

13. The product obtained by the method described in claim 6.

14. The product claim 7.

obtained by the method described in obtained by the method described inobtained by the method described in Greenlee Sept. 12, 1950 De GrooteApr. 24, 1956

1. THE METHOD OF (A) CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE,FUSIBLE, NON-OXYGENATED ORGANIC SOLVENTSOLUBLE, WATER-INSOLUBLE,LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHTCORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESINMOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TOMETHYLOLFORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEENA DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED INTHE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OFTHE FORMULA